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On the Structure of the Helmholtz Layer and its Implications on Electrode Kinetics

Lewerenz, H. J. (2013) On the Structure of the Helmholtz Layer and its Implications on Electrode Kinetics. ECS Transactions, 50 (52). pp. 3-20. ISSN 1938-5862. doi:10.1149/05052.0003ecst.

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Concepts and selected experiments on the structure of the Helmholtz double layer at the metal- and semiconductor - electrolyte phase boundary are reviewed. The widely used microcapacitor approach of the double layer and its limitations are assessed. Observations on the influence of the electrode potential on the energetic position of surface states at the Ag-electrolyte contact are compared to the predictions of classical charge transfer models that are based on transition state theory where adiabatic tunneling is assumed. Distance tunneling spectroscopy on Au(111) surfaces shows pronounced variations in tunneling barrier heights that are connected to the inner structure of the Helmholtz layer and implications on electrode kinetics are presented. At the semiconductor-electrolyte contact, the influence of the electrode potential on a charge injecting species that results in photocurrent doubling is reviewed for low- and higher doped Si(111) electrodes, showing that the complex that injects electrons into the conduction band is located outside the semiconductor surface. The observations are correlated with the search for low overpotential earth abundant electrocatalysts for solar fuel generation of solar fuels.

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle
Lewerenz, H. J.0000-0001-8433-9471
Additional Information:© 2013 Electrochemical Society. Support by the DFG, project LE 1192-4 and by the Joint Center for Artificial Photosynthesis is gratefully acknowledged. Dedicated to the memory of Dieter M. Kolb.
Funding AgencyGrant Number
Deutsche Forschungsgemeinschaft (DFG)LE 1192-4
Joint Center for Artificial Photosynthesis (JCAP)UNSPECIFIED
Subject Keywords:Helmholtz layer structure, electrochemical kinetics, electroreflectance, distance tunneling spectroscopy, electron injection, transition state concept
Issue or Number:52
Record Number:CaltechAUTHORS:20140312-093801401
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Official Citation:On the Structure of the Helmholtz Layer and its Implications on Electrode Kinetics Hans Joachim Lewerenz ECS Trans. 2013 50(52): 3-20; doi:10.1149/05052.0003ecst
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44273
Deposited By: Ruth Sustaita
Deposited On:12 Mar 2014 17:45
Last Modified:10 Nov 2021 16:50

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